CA1072853A - Laundry detergent composition and use - Google Patents
Laundry detergent composition and useInfo
- Publication number
- CA1072853A CA1072853A CA267,486A CA267486A CA1072853A CA 1072853 A CA1072853 A CA 1072853A CA 267486 A CA267486 A CA 267486A CA 1072853 A CA1072853 A CA 1072853A
- Authority
- CA
- Canada
- Prior art keywords
- zeolite
- sodium
- molecular sieve
- detergent composition
- carboxymethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2089—Ether acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Abstract of the Disclosure A heavy duty laundry detergent composition, preferably a non-phosphate detergent of improved cleaning power, includes certain proportions of molecular sieve zeolite, preferably partially hydrated type 4A molecular sieve zeolite, sodium carboxy-methyl-oxysuccinate (CMOS), sodium linear higher alkylbenzene sulfonate, higher fatty alcohol polyethoxylate, sodium silicate and anti-redeposition agent. The product has better soil removal properties than those of compositions like it but wherein the CMOS is replaced by sodium tripolyphosphate, sodium citrate or sodium tartrate, and is also superior to similar products wherein the mixture of CMOS and zeolite is re-placed by equal weights of sodium tripolyphosphate, zeolite of CMOS. Usefully detersive products of the invention omit inorganic phosphate builder salt with-out loss of cleaning ability (in fact, some improvement is noted) and contain reduced proportions of molecular sieve zeolite, so as to diminish any problems associated with the deposition of such zeolite on laundry and the resulting objectionable muting of colors of the laundered fabrics. Also described are methods of laundering in which the invented compositions are used.
Description
~L~7Z~53 This invention relates to heavy duty laundry detergent compositions. More particularly, it relates to such compositions which include s~dium carboxymethyl-oxysuccinate (C~IOS), molecular sieve zeolite, linear higher alkylbenzene sulfonate, sodium silicate and anti-redeposition agent, which have better soil removal properties than those of similar compositions which contain pentasodium tripolyphosphate instead of CMOS. ~he invented compositions preferably also include a higher fatty alcohol polyethoxylate nonionic detergent and omit any phosphate builder saLts and other phosphorus-containing compounds. Also within the invention are methods of washing fabrics with the invented compositions. -In recent years much attention has been given to the problem of formulating satisfactory heavy duty laundry detergents without utili~ing phosphates. Because o~ claims that phosphorus sometimes cause eutrophication of inland waters legislation has been passed in various ~urisdictions limLting the contents thereof in detergent compositions. Pentasodium tripolyphosphate has been the most successful commercial builder salt for synthetic anionic orga~ic detergent compositions and therefore : '' .- . .
- -, - 1 - , ~7Z853 replacement of it has been especially difficult. Among the products that have been suggested for use as builders for heavy duty laundry detergents are sodium carboxymethyl-oxysuccinate (CMOS) and molecular sieve ~eolites, such as partially hydrated type 4A molecular sieve zeolites. The latter compounds are water-insoluble and act to sequester or tie up soluble calcium ions in wash waters, thereby allowing the synthetic organic detergent component of heavy duty laundry detergent compositions to wet and emulsify lipophilic soils on the garments, articles and fabrics to be cleaned, without interference from the calcium present. Xowever, it has been noted that when laundry washed with detergent compositions containing a sufficient proportion o~ molecular sieve zeolite to be almost as effective as the usual phosphate-containing detergents is line dried, rather than dried in an automatic laundry dryer, a noticeable quantity of the molecular sieve zeolite is retained in the articles laundered, which is ob~ectionable.
CMOS is a soluble organic builder which i9 a good 8equestrant ~or calcium ion. However, as with various other synthetic organic builders, it is comparatively expensive and the use o~ a sufficient quantity thereo~ to produce essentially the same extensive soil removal as the usually desirable :
proportion of pentasodium tripolyphosphate may so increase the cost of the product as to make it commercially non-competitive.
Also, some handling characteristics, such as flowability, ~., ' 8~3 norl-tackiness and non-caking are effected adversely. IIowever, in the present compositions, generally containing about equal proportions of molecular sieve zeolite and CMOS, together with usually lesser proportions Or linear higher alkylbenzene sulfonate detergent, sodium silicate, as a supplementary builder and anti-corrosion agent, and anti-redeposition agent, a superior product is obtained, having better soil removing properties than comparable formulations containing sodium tripolyphosphate, molecular sieve zeolite or CMOS in place Or the combination of molecular sieve zeolite and CMOS or contain-ing a mixture of about equal parts of molecular sieve zeolite and pentasodium tripolyphosphate. The invented formulation is also significantly superior in cleaning power to zeolite~
citrate and zeolite-tartrate mixtures, with the same pr~portions being employed, the essential substitution being that of the citrate or t~trate for CMOS. Thus, a commercially competitive heavy duty laundry detergent of better cleaning properties i5 made in accordance with this invention and i3 free M owing, non-tacky and non-caking. The molecul~r sieve zeolite helps to make up for the absence of pentasodium tripolyphosphate in both calcium sequestering po~er and in promoting flowability and it compensates for the presence of the CMOS in the formNla with respect to flowability. Also, CMOS and silicate in the deter- :
gent prod~ct formulation help to sequester magnesium ions while the molecular sieve zeolite acts most effectively against .
~72853 calcium ions. Of course such activities are important because both calcium and magnesium ions are found in most hard waters.
In accordance with the present invention a heavy duty laundry detergent comprises 15 to 20% by weight of a water insoluble molecular sieve zeolite selected from the group consisting of A, X, Y, L, mordenite and erionite and containing from about 1.5% to about 36% by weight of water, said zeolite having a cation selected from the group consisting of sodium, potassium, lithium, ammonium and hydrogen and having a mean particle diameter of about 0.5 to about 12 microns, 15 to 20% of a carboxymethyl-oxysuccinate selected from the group consisting of water soluble alkali metal salts thereof and mix- -tures of said salts containing some unneutralized carboxymethyl-oxysuccinic acid; 5 to 25% of linear higher alkylbenzene sulfonate wherein the higher alkyl is of 10 to 16 carbon atoms; 3 to 18% of sodium silicate wherein the Na20:SiO2 ratio is in the range of 1:1 to 1:3.2; and 0.3 to 3% of an organic anti-redeposition agent selected from the group consisting of carboxymethyl cellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, lower alkyl cellulose and hydroxy-lower alkyl lower alkyl cellulose. In preferred aspects of the invention the molecular sieve zeolite is a hydrated or partial-ly hydrated type 4A molecular sieve zeolite~ in which the sodium aluminosili-cate is of SiO2:A1203 ratio of about 2 (on a molar basis, about one atom of silicon per atom of aluminum), the carboxymethyl-oxysuccinate is sodium carboxy-methyl-oxysuccinate, the linear higher alkylbenzene sulfonate is sodium tri-decylbenzene sulfonate, the sodium silicate is of Na20:SiO2 ratio of about 1:2.4, the anti-redeposition agent is sodium carboxymethyl cellulose and also contained is about 0.5 to 20% of higher fatty alcohol polyethoxylate having 6 to 15 ethoxy groups per mol and wherein the alcohol is of 12 to 18 carbon atoms and about 0.5 to 2% of sodium higher fatty acid soap wherein the higher fatty acid is of 12 to 18 carbon atoms.
- 4 ~
~7Z853 Also within the invention are methods of using the detergent compositions in washing laundry and fabrics.
The molecular sieve zeolites utilized in making the invented deter~ent compositions are water insoluble crystalline alluminosilicate zeolites of natural or synthetic origin which are characterized by having a network of uniformly sized pores in the range of about 3 to 10 Angstroms, preferably about ~ A
(nominal), which size is uniquely determined by the unit structure of the zeolite crystal. Of course, zeolites containing two or more such networks of different size pores can also be employed.
The molecular sieve zeolite should also be a univalent cation-exchanging zeolite, i.e., it should be an alumino-silicate containing a univalent cation such as sodium, potassium or lithium, when practicable, or of ammonium or hydroeen.
Preferably, the univalent cation associated with the zeolite molecular sieve is an alkali metal cation, especially sodium or potassium, most preferably sodium.
Crystalline types o~ zeolites utilizable as molecular sieves in the invention, at least in part, include zeolites o~
the following crystal structure groups: A, X~ Y, L, mordenite and erionite. Mixtures of such molecular sieve zeolites can also be useful, especially when type A zeolite, e.g., type ~A, is present. These preferred crystalline types of zeolites are well known in the art and are more particularly described in the text, Zeolite Molecular ~ieves, by Donald W. Breck, ~6~721~53 published in 1974 by John Wiley & 50ns. Typical commercially available zeolites of the aforementioned structural types are listed in ~able 9.6 at pages 747-749 of the Breck text.
Preferably the ~olecular sieve zeolite used in the invention is a synthetic molecular sieve zeolite. It is also preferable that it be o~ type A crystalline structure, more particularly described at page 133 of the aPorementioned text.
Especially good results are generally obtained in accordance with the invention when a type 4A molecular sieve zeolite is employed, wherein the univalent cation of the zeolite is sodium ~-and the pore size of the zeolite is about 4 Angstroms. The especially pre~erred zeolite molecular sieves are described in United States patent 2,882,243 which refers to them as Zeolite A.
Molecular sieve zeolites can be prepared in either a dehydrated or calcined form, the latter ~orm containing ~rom less than about 1.5% to about 3% of moisture, or in a hydrated or water loaded ~orm, which contains additional water of hydration and adsorbed water in sn amount up to about 30 to 36%
of the zeolite total weight, depending on the type of zeolite employed. Normally a completea hydrated type 4A synthetic zeolite will be o~ the ~ormula ( a20)6 (A1203)6 (SiO2)12 27 H20 or Nal2(A102 Si2)12 27 H2 . , .
: ~
- 6 - ~
` ~' : .
, ~al72853 when completely molecularly hydrated. ~owever, this product can still adsorb or absorb additional moisture so that the upp~r limit in moisture content is not about 22%,as calculated, but may be higher. Preferably, hydrated or partially hydrated ~orms of the molecular sieve zeolite are employed in the practice of this invention and these usually have a ~ater content of 18 to 28.5%, e.g., 20 to 22%. The manufacture of such crystals is well known in the art. For example, in the preparation o~ 1 Zeolite A, referred to above, the partially hydrated or hydrated zeolite crys-tals that are formed in the crystallization medium (such as hydrous amorphous sodium aluminosilicate gel) are made without the high temperature dehydration (calcining to 3% or ~ `
less water content) that is normally practiced in preparing such crystals for use as catalysts, e.g., cracking catalysts. The preferred form of zeolite in partially ~ydrated ~orm can be recovered by filtering o~f the crystals from the crystallization n~edlum and drying them in air at ambient temperature to ~luch an extent that the water content thereof is as desired.
Usually the molecular sieve zeolite should be in finely divided condition, such as crystals (amorp~ous or poorly crystalline p~rticles may also ~ind some use) having mean particle diameters in the range of about 0.5 to about 12 microns, preferably 5 to 9 microns and especially about 5.9 to 8.3 microns9 e.g., 6.4 to 8.3 microns.
The CMOS constituent o~ the present detergent compositions, carboxymethyl-oxysuccinate, normally employed as 1~7Z85.~
a water soluble salt, such as an aIkali metal salt, e.g., sodium carbox~methyl~oxysuccinate. ~he degreeofneutralization oP this supplementary builder may vary and in some cases some unneutralized carboxymethyl-oxysuccinic acid may be present.
However, normally the carboxyl groups will be converted to sPlt form before formulation of the detergent ~roduct, during such formulation or during washing with the composition. All the carboxyls of the CMOC are preferably neutralized, as with a sodium-containing base, to make them more effective as calcium sequestrants but it is within this invention to utilize partially neutralized CMOS, too. Thus, the mono- and di-salts and mixtures averaging mono-, di- and intermediate salts (including those intermediate di- and tri-) are also utilizable. While C~IOC in its sodium salt form i9 highly preferred as the auxiliary builder of this invention which cooperates with the zeolite and silicate to give the present detergent products superior properties, it is also contemplated that the CMOC may be substituted in part, e.g., up to 50%, by other builders of similar chemical structure. Thus, instead of the carboxymethyl-oxy substitution on the succinic acid, carbox~ethyl-oxy, carboxypropyl-oxy and carboxyisopropyl-oxy substitutions may be utilized and instead of succinic acid, comparable acidic compounds such as malonic acid, glutaric acia and adipic acid, may be employed (with the different substitutents on such acids, too) so long as they are operative. However, the _ 8 -.
.
.
~72853 use of CMOS is highly preferred and it will normally be employed as a sodium salt, preferably the trisodium and/or disodium salt.
The linear higher alkylbenzene sulfonate deter-gent will usually b e of 10 to 16 carbon atoms, preferably 12 to 14 carbon atoms and most preferably about 13 carbon atoms and will normally be neutralized with a suitable alkaline mate-rial, of which the most preferred are such s~hich result in alkali metal linear higher alkylbenzene sulfonates being produc-ed, preferably the sodium salts of the linear higher alkyl-benzene sulfonic acid. Other synthetic anionic organic deter- ;
gents may be present with the linear higher alkylbenzene sul-fonates but normally will only constitute a minor proportion of the total anionic detergent content of the present compositions.
Such supplementing anionic detergents may be of 8 to 26, preferably 12 to 22 carbon atoms per molecule and usually will include an alkyl or other aliphatic chain containing about 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms and most preerably will be straight chain alkyl. Such anionic detergents include the alpha-olefin sulfonatesJ paraffin sulfonates, ethoxy-lated alcohol sulfates, alkyl sulfates and sulfated higher alkyl phenyl polyoxyethylene ethanols, all preferably as alkali metal salts, such as the sodium salts. A list of such detergents is found in United States patent 3,~37,339. The water soluble higher fatty acid soaps, such as the sodium soaps of higher fatty , ~. . .
_ g _ , .~ .
~)728S3 acids of 12 to 18 carbon atoms may also be employed as anionic detergents in the present compositions.
Nonionic detergent compounds are often utilized in the present detergent compositions in mixture with a linear higher alkylbenzene sulfonate de-tergent and with any other suitable supplementing anionic detergent present. The nonionics will normally be lo~er aIkylene oxide condensation products, such as polyethylene oxides, which may sometimes have polypropylene oxide present too but only to such an extent that the product is still wat.er soluble. Preferred examples of such materials are the higher fatty alcohol-polyethylene oxide condensates wherein the higher fatty alcohol is of 10 to 18 carbon atoms, preferably 12 to 15 carbon atoms and the ethylene oxide portion thereof is a chain of 3 to 30 ethylene oxide units, preferably 6 to 15 ethylene oxide units and more preferably, about 10 to 13 ethylene oxide units. For example, a preferred nonionic detergent of this type is Neodol*45-11, manu~actured by Shell Chemical Comp~ny, wh~ch i6 a hi~her fatty alcohol polyethoxy-ethanol containing about 11 ethylene o~ide groups per mole (includin~ the ethoxy of the ethanol) ~nd having an average of about 14 to 15 carbon atoms in the higher fatty alcohol. Other primary alcohol condensation products include Plurafac*B-26 and Alfonic*1618-65. ~ergitol*15-S-9, made by Union Carbide Corpora-tion, exemplifies the suitable secondary alcohol condensation products with ethylene oxide. Also useful are similar ethy].ene oxide condensates of phenols, such as of nonyl phenol or isooctyl phenol, knoun as Igepals*, made by GAF Corporation, but these are not preferred.
In the present compositions there may also be em-ployed any o~ a number o~ suitable amphoteric and cationic detergents *Trademark - 10 -, . - . : - --~L~7Z85~
which are well known and, like the snionic and nonionic detergents, builders, adjuvants and other intended components of the present compositions, are described in the text Surface Active Agents and Detergents, Vol. II, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, Inc., especially at pages 25-138, and in Deter~ents and Emulsifiers, 1969-1973 Annuals, by John W. McCutcheon.
The sodium silicate component of the invented composition is one of Na20:SiO2 ratio in the range of 1:1 to 1:3.2, preferably 1:2 to 1:2.6 and most preferably about 1:2.4, e.g., 1:2.35. Such a compound is especially useful in -the present compositions for its combination anti-corrosion and building effects in con~unction with the zeolite molecular sieve and CMOS. The silicate is espec~ally good as a builder in wash waters containing magnesium ions and thereby usefully complements the other builder materials under u5ual washing conditions.
The w3e of an anti-redepositLon agent in the invented compositions is especially important because o~ the presence in the wash waters of insoluble, depositable particulate ma~erial, including the molecular sieve zeolite. Of the known anti-redeposition agents the most preferable to employ is sodium carboxymethyl cellulose but also useful, either as partial or complete substitutes for the sodium carboxymethyl ~ ;
cellulose (and only minor substitution is preferred) are ~
-- 11 -- , ~Lal728S3 polyvinyl alcohol, pol~vinyl acetate (which hydrolyzes to the alcohol), polyvinyl pyrrolidone, lower alkyl celluloses, e.g., methyl cellulose, ethyl cellulose, and hydroxy-lower alkyl lower alkyl celluloses, e.g., hydroxypropyl methyl cellulose, hydroxyethyl ethyl cellulose. In such latter cellulose compounds the lower alkyl groups are usually of 1 to 3 carbon atoms.
In addition to the molecular sieve zeolites, CMOS
and silicate, other builder salts may also be present in the invented compositions. Normally these are water soluble and are alkali metal salts, preferably the sodium and potassium salts o~ inorganic acids3 e.g., sodium carbonate, potassium bicarbonate~ borax, pentasodium tripolyphosphate and tetra-sodium pyrophosphate. However, the phosphates and borax are often preferably omitted ~or ecologica]. reasons. Organic builders may also be utilized in the present compositions, such as trisodium nitrilotriacetate or NTA (which is still not approved for general use in detergents~, sodium citrate, potassium gluconate and hydroxyethyl iminodiacetate, disodium salt. 0~ course, ~iller salts, such as sodium sul~ate and sodium chloride, are normal constituents o~ detergent composi-tions and may be employed. -Various ad~uvants may be present for their special activities, such as enzymes, e.g., proteolytic enzymes (proteases) and amylotic enzymes (amylase); hydrotropes, e.g., sodium toluene sulfonate; wetting agents; flow-improving , :: ' ' :, .
1~7Z~35;~
agents, e.g., clays ~although the molecular sieve zeolite usually performs such functions satisfactorily in the proportion employed); bactericides, fungicides, fluorescent brighteners;
dyes; pigments; perfumes; emollients; stabilizers; fillers;
coating agents; and softeners. When bleachesJ e.g., sodium perborate, sodium percarbonate, and activators for bleaching are used they will usually be present in greater quantities than other adjuvants.
The proportions of the various components of the invented compositions should be held within the following described ranges for good activities. The product should com-prise ~and often may consist essentially of)preferably 15 to 20% of molecular sieve zeolite, more preferably about 17%;
tlle same ranges of percentages for CMOS; 5 to 25% of linear i`
higher alkylbenzene sulfonate, preerably 8 to 12% and more preferably about 10%; 3 to 18% of sodium silicate, preferably 5 to 15% and more preferably about 8%; and 0.3 to 3%J pre-ferably 0.3 to 1% and more preerably about 0.5~ of anti-redeposition agent. The ratios of molecular sieve zeolite :
CMOS : linear higher alkylbenzene sulfonate ; sodium silicate : -anti redeposition agent will usually be in the range of 1 : 0.5 to 2 : 0.2 to 1 : 0.3 to 2 : 0.02 to 0.2, preferably 1 : 0.7 to 1.2 : 0.4 to 0.8 : 0.3 to 0.7 : 0.02 to 0.1 and most pre-ferably about 1 : 1 : 0.6 : 0.5 : 0.03. When nonionic detergent is present in the formulation :-.... .
~ 13 -- ~
1~:97Z853 it will normally be ~rom 0.5 to 20% o~ the product, preferabl~ 0.5 to 2.5%
thereof and most preferably will ~e about 2~. When soap is present it will usually be in a proportion from 0.3 to 3%, preferably 0.5 to 2% and most preferably about 1%. Filler content will generally be in the range of 15 to 60%, preferably 25 to ~5% and most pre~erably about 35%. Moisture content may be from 0.5 to 15%, usually being 2 to 10% and preferably 3 to 8%, e.g., 7%, as "free moisture".
Any usual adjuvants present will normally total about 1 to 10%, with individual ad~uvants generally being in the range of 0.01 to 5%. For example, the content of fluorescent brighteners or optical dyes may be in the range o~ 0.01 to 2%, normally being about 0.5 to 1.5%. The t ~ of ad~uvants is preferably in the range of 1 to 5%, such as 2 to ~% and typical-ly about 2.5% thereof may be present and will include perfumes, colorants, flow promoting compounds and optionally, fungicides, bactericides and emol-lients. I~ bleaches are present in these detergent compositions they will normally be from 5 to 30%, including activators for bleaching percompounds, and the~proportions of other components will ble reduced accordingly. Of course, mlxtures of dif~erent types of individ~ual components within the in-vention may be used, too.
~he various components of the detergent compositions m~y be blended together by admixing powdered compounds but preferably crutcher mixes of most of the components are spray dried, spray cooled, drum dried or otherwise converted to globular "spray dried" form. Alternatively, various components may be co-size-reduced to the desired particle size ranges. ~ormally, per-fume, nonionic detergent, flow promoting agent and any heat-sensitive com-porents will be post-added to tumbling spray dried detergent composition.
However, in some cases it may be desirable to promote ~low of tbe product by post-adding a proportion of the molecular sieve zeolite, e.g., 10 to 25% of the amount o~ molecular sieve ~eolite in the final product The globular particles of detergent compositions may be classified or sieved so that over 90%, preferab.~y over 95% and most preferably, all tbereof passes through a ~o. 8 or No. 10 United States Standard Sieve Series sieve and less than 10%, : ' . . : , ~7;~8'~3 pre~erably less than 5% and most preferably, 0% passes through a No. 100sieve. The rest of the product, which may be post-added, if in the solid state, will normally be in powder form, with the molecular sieve zeolite powder component being of the size previously mentioned, e.g., from 5 to 9 microns in diameter, and the other po~dered products being such that they will pass through a ~o. 100 sieve and fail to pass a ~o. I~oo sieve, pref-erably pasfing through a No. 1~0 sieve and resting on a No. 325 sieve. When the nonionic detergent is in liquid form or may be readily liguefied, it may be desirable to spray it onto the surfaces of the tumbling detergent globule-powder mixture.
The washin~methods of this invention may be carried out at various pH's and concentrations of the detergent composition in washing liquid medium but normally the pH will be in the range of 8 to 12, preferably 8.5 to 10.5 ancl most preferably 9 to 10.5. The concentration of the detergent composi-tion in the aqueous washing medium, which will usually be ordinary tap water, will normally be from 0.05 to 2%, preferably being about 0.1 to 1%. Most preferably, such concentration will be about 0.15% in the United States and abo~lt o.8% in European countries wherein high concentrations of detergent and low volumes of wash water have been employed in the conventional washin~
machines. Usually the laundry : wash water ratio will be from 0.03 to 0.2, preferabl~ 0.04 to 0.1~ e.g., 0.05 or o.o6 for United States laundry practices and about one to five times these ra-tios, e.g., about three times such rat~os, for European practices. ~aterials washable with the invented com-positions include cottons, polyesters, cotton-polyester blends, e.g., 55:45 blends, permanent press fabrics and all usual commercial fabrics.
~he present compositions are employed in the same manner as com-parable commercial heavy duty laundry detergents. Thus, they may be used for cold, warm and hot water washing, usually in the temperature range of 10 to 70 C. Excellent cold and warm water washings of ~arious types of fabrics result, using ordinary automatic washing machines and normal washing times, 3 to 45 minutes, preferably being from 5 to 20 minutes in the United States and from 20 to 40 minutes according to European practices.
, ,. , . : :. . .
1~72853 Various advantages of the invented compositions have already been mentioned. The presence of the molecular sieve zeolite appears to help to prevent staining o~ ~hite or light goods ~ith stains which might be removed from colored goods or laundry containing colored soils. In such cases, in the presence of the CMOS and other detergent composition constituents, the molecular sieve zeolites appear to preferentially adsorb the color bodies ;
and thereby prevent them from being deposited on the white or lighter colored goods, resulting in a lesser amount of discoloration thereof. Also, the lowered content of molecular sieve zeolite results in less deposition thereof on the clothing and the proportion of anti-redeposition agent present is capable of maintaining most of the molecular sieve zeolite in suspension in the wash water so that it does not become entrapped in the fabrics being cleaned (which could occur during rinsing). The presence of the linear alkylbenzene sulfonate detergent appears to assist in maintaining the sus-pension of the molecular sieve zeolite, too. Of course, the combination of various types of builders which are "sequestrants" for different types of h~ dnesses favors ~etter wnshing by the anionic detergent (and accompanying nonionic detergent, when employed). Thus, there are sienificant coactions between the various components in the proportions in which they are employed in the present detergent compositions.
~ he invention will be further illustrated by the following ex-amples. Unless otherwise indicated all parts therein and in the specifica-tion are by weight a~d all temperatures are in C.
EXA~PIE 1 A preferred detergent composition of this invention is made by spray drying an aqueous crutcher mix of the components thereof and containing about 60% of solids, in a countercurrent spray tower utilizing drying air at about 250 C,, to a moisture content of about 6.5% and then spraying 0.5% of perfume onto tumbling surfaces thereof. The perfumed spray dried detergent composition includes, on a final product basis, about 10% of sodium linear tridecyl benzene sulfonate, 17% of type I~A molecular sieve zeolite (the SiO2:A1203 mol ratio of which is 2 and which contains 20% of moisture, is of ~`~
- ~:
~C~7;Z~Si3 pore sizes of about 4 ~ gstroms diameter and is of particle si~es in the range of 5.9 to 803 microns in diameter), 17% of sodium CMOS (trisodium salt), 0.5% of sodium carboxymethyl cellulose, 2% o~ ~eodol ~5-ll (higher :-fatty alrohol polyethoxyethanol of about ll ethoxy groups per mol and in which the higher fatty alcohol is of 14 to 15 carbon atoms per mol), 1% of higher fatty acid soap ~herein the higher fatty acid i5 a mixture of hydro-genated coconut oil ana hydrogenated tallow in 1:4 ratio, 35% of sodium sulfate (as the anhydrous form), 8%of sodium silicate (Na20:SiO2 = 1:2.35) and about 3% of various ad~uvants (fluorescent brighteners, perfume, stabili2er, free oil [impurities in materials charged] and colorants). The particle sizes of the spray dried beads are in the range of lO to 100 mesh, United States Standard Sieve SPries. The CMOS, sulfate and CMC, as charged to the crutcher, are powders of particle sizes such that they pass through a No. 140 sleve and rest on a No. 325 sie~e, United States Standard Sieve Series.
The detergent composition made i8 substantially homogeneous, free-flowing and non-dusting, possibly in part due to the adsorption cf any excess moisture in the spra~ dried product by the zeolite molecular sie~e. Also, the product is substantially non-tacky and non-caking under ordinary storage conditions.
In test washing of mixed laundr~ having an artificial test soil deposited thereon, whlch laundry is composed of' test swatches of cotton, cotton-polyester and permanent press treated cotton-polyester fabrics, the detergent concentration in the wash water is 0.15%, the water employed has 150 parts per million of hardness (the clacium : magnesium hardness ratio, calculated as calcium carbonate, being 3:2), the temperature is maintained at 49C. and washing is continued for ten minutes in a laboratory Tergo-tometer ~ washing machine. At the end of washing the wash water has a pH
of 9.2. The test f`abrics washed are rinsed and dried in the normal manner and are read for whiteness (Rd on the Gardner Color Difference Meter). The Rd for the pre~erred experimental composition described is 50Ø Thls indi-cates that the cleaning power of the detergent composition is superîor to : . . . , . , . . : . .
~a~7z853 that of a similar composition, made the same way~ in which the combinationof the molecular sieve ~eolite and CMOS is replaced by an equal weight of pentasodium tripolyphosphate ( Rd = 48.7); the molecular sieve zeolite ( Rd = 45.9); CMOS ( Rd = 48.5); equal parts of type 4A molecular sieve zeolite and of pentasodium tripolyphosphate ( Rd = 46.8); equal parts of the molecular sieve zeolite and of sodium citrate ( Rd = ~.5), and equal parts of the molecular sieve Peolite and sodium tartrate ( Rd = 41.0).
In practical laundry tests the preferred composition is also especially useful in removing various types of soils from the lalmdry. How-ever, in such tests the water temperature ranges from 15 C. to 65C., thehardness thereof is from 50 to 250 parts per million of calcium carbonate (mixed clacium and magnesium hardness), the washing times are from 5 to ~5 minutes, the machines employed are top loading and side loading, the deter-gent composition : laundry weight ratio is from 0.01 to 0.1 and the laundry :
wash water ratio is from 0.03 to 0.2. No ob~ectionable deposits of molecular sieve zeolite are found on laundry which is machine washed and subsequently line dried and of course, no such deposits are found on such laundry which is dried in an automatic clothes dryer.
The whitening power of the composition can be further improved by replacing half of the quantity Or sodium sulfate present (17.5%) with penta-sodiu~ tripolyphosphate, when such compound may be employed without violation of l&w and without adverse effects on the ecology. Apparent brightness is improvable when fluorescent brighteners are included in the formula as part of the ad~uvant composition, especially when there is present a stilbene fluorescent brightening compound, such as Tinopal ~ RB~ (Geigy), preferably with Tinopal 5B~I Conc. in lesser proportion, the total proportion of the ;
fluorescent brighteners being about 1%. Stain removal and soil removal are also improved by the addition to the composition of about 1% of Alcalase ~ ;
proteolytic enzyme. Further useful effects in removing stains and soils are obtainable when a per compound such as sodium perborate tetrahydrate is present, usually as a ma~or replacement for the sodium sulfate, e.g., con-stituting about 20% of the detergent product. Such perco~pound is post-.`' :
' . ' ' ' ' ' ': '' .- ~: ~ ' ~7z1353 added to the spray dried product.
In variations of the above formula for the preferred invented product the ~eodol and soap are omitted. In such cases the invented com-positions are still better in washing effects than the various controls described, from ~hich such components have also been removed. In other variations of the formulation 20% of the linear aIkylbenzene sulfonate con-tent is replaced by sodium higher fatty alcohol sulfate in one experiment, 30% of it is replaced by sodium paraffin sulfonate in another case and in another instance 25% of it is replaced by alphaolefin sulfonate of essen-tially the same chain length. In all such cases satisfactory detergents of .
desirable characteristics, such as those described, are obtained. Such isalso the situation ~Then the proportion of sodium silicate present is in-creased to 15% in the final product.
The compositions of Example l are made but with the substitution of type ~A molecular sieve zeolite which i9 completely molecularly hydrated (22%
of water of crystallization, corresponding to 27 mols H20 per mol zeolite), partially hydrated such molecular sieve zeolite containing about half as much of water o~ hydration and an anhydrous type 4A molecular sieve zeolite. Use-ful detergent products result in all such cases.
The compositions oP this example are ~urther varied by replacin~
the trisodium CMOS employed with disodium CMOS ~nd with monosodium CMOS and by partially replacing it (20%) with carboxymethyl-oxysuccinic acid. UsePul detergents of desirable cleaning power are also obtained. ~;
.. .
In a further variation of these formulas sodium silicates of '. :'' ...
~a20:SiO2 ratios oP 1:2.0 and 1:2.6 are employed and good detergents sim-ilarly result. ~his is also the case ~hen sodium carboxgmethyl cellulose is replaced, to the extent of half the content thereof, with polyvinyl alcohol, ~ `
polyvin~l pyrrolidone~ hydroxypropylmethyl cellulose and methyl cellulose, respectively. ~owever, it is considered that sodium CMC makes the best detergents, those having the best soil anti-redeposition properties, and therePore it is preferred to use it alone.
. ' ' ~:, `
.
~0~28S3 Instead of the type 4A molecular sieve zeolite there are sub-stituted the same quantities of types X and Y molecular sieve zeolites in the formulas of Examples 1 and 2. The products resulting are useful deter-gents by the tests described but for best detereency and physical properties it is considered most desirable to utilize the type 4A molecular sieve zeolite which is either hydrated or partially hydrated~ Anhydrous forms of the various zeolites, unless they are hydrated during the manufacture of the detergent composition, take additonal time durine the washing operation to be hydrated first before they are able to effectively carry out their seques-tering and building functions. Thus, they take longer to act and therefore may be less effective in some instances.
The proportions of the various components of the compo~itions of Examples 1-3 are varied within the ranges and ratios given in this specifica-tion, normally beine chan~ed -30%, ~ 0% and -10%, within such ranges. ~he products made are useful detergents, suitable for employment in various cleaning operations. Of such detergents, those which contain no phosphorus or are sub3tantially free of phosphorus (usually containing less than 1% of phosphorus) are preferred, to comply with anti-eutrophication laws and reg-ulations. --~ he formulations of the previous examples are mndified by replacing the nonionic detergent, when present, with a comparable nonionic detergent, Plurafac B-26 ana alternatively~ with Alfonic 1618-65. In variations of the manufacturing proceduse, the nonionic detergent is melted and sprayed onto the surfaces of the tumbling spray dried components. GoGd detergents result. -i ~his iB also the csse when half of the sodium sulfate filler content is re-placed by sodium chloride. In other variations of the manufacturing methods the molecular sieve, C~OS and ~MC are post-added to spray dried besds of the rest o~ the product components and the detergent composition resulting is also superior to control compositions based on pentasodium tripolyphosphate _ 20 -. , - : , . ~ :. . .
(wheretn the STPP is present in quantity equal to the sum of the CMOS and molecular sieve zeolite). The detergent composition is also made by co-size-reducing the various powders to the 10 to 100 mesh range (the zeolite adhering to the larger sized particles). The products so made are also acceptable detergents, comparable in performances to those previously described and superior to the various controls mentioned.
!~ -The invention has been described with respect to various illustra-tions and embodiments thereof but is not to be limited to these because it is evident that one of skill in the art will be able to use substitutes and equivalents without departing from the spirit of the invention.
... . . .
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- -, - 1 - , ~7Z853 replacement of it has been especially difficult. Among the products that have been suggested for use as builders for heavy duty laundry detergents are sodium carboxymethyl-oxysuccinate (CMOS) and molecular sieve ~eolites, such as partially hydrated type 4A molecular sieve zeolites. The latter compounds are water-insoluble and act to sequester or tie up soluble calcium ions in wash waters, thereby allowing the synthetic organic detergent component of heavy duty laundry detergent compositions to wet and emulsify lipophilic soils on the garments, articles and fabrics to be cleaned, without interference from the calcium present. Xowever, it has been noted that when laundry washed with detergent compositions containing a sufficient proportion o~ molecular sieve zeolite to be almost as effective as the usual phosphate-containing detergents is line dried, rather than dried in an automatic laundry dryer, a noticeable quantity of the molecular sieve zeolite is retained in the articles laundered, which is ob~ectionable.
CMOS is a soluble organic builder which i9 a good 8equestrant ~or calcium ion. However, as with various other synthetic organic builders, it is comparatively expensive and the use o~ a sufficient quantity thereo~ to produce essentially the same extensive soil removal as the usually desirable :
proportion of pentasodium tripolyphosphate may so increase the cost of the product as to make it commercially non-competitive.
Also, some handling characteristics, such as flowability, ~., ' 8~3 norl-tackiness and non-caking are effected adversely. IIowever, in the present compositions, generally containing about equal proportions of molecular sieve zeolite and CMOS, together with usually lesser proportions Or linear higher alkylbenzene sulfonate detergent, sodium silicate, as a supplementary builder and anti-corrosion agent, and anti-redeposition agent, a superior product is obtained, having better soil removing properties than comparable formulations containing sodium tripolyphosphate, molecular sieve zeolite or CMOS in place Or the combination of molecular sieve zeolite and CMOS or contain-ing a mixture of about equal parts of molecular sieve zeolite and pentasodium tripolyphosphate. The invented formulation is also significantly superior in cleaning power to zeolite~
citrate and zeolite-tartrate mixtures, with the same pr~portions being employed, the essential substitution being that of the citrate or t~trate for CMOS. Thus, a commercially competitive heavy duty laundry detergent of better cleaning properties i5 made in accordance with this invention and i3 free M owing, non-tacky and non-caking. The molecul~r sieve zeolite helps to make up for the absence of pentasodium tripolyphosphate in both calcium sequestering po~er and in promoting flowability and it compensates for the presence of the CMOS in the formNla with respect to flowability. Also, CMOS and silicate in the deter- :
gent prod~ct formulation help to sequester magnesium ions while the molecular sieve zeolite acts most effectively against .
~72853 calcium ions. Of course such activities are important because both calcium and magnesium ions are found in most hard waters.
In accordance with the present invention a heavy duty laundry detergent comprises 15 to 20% by weight of a water insoluble molecular sieve zeolite selected from the group consisting of A, X, Y, L, mordenite and erionite and containing from about 1.5% to about 36% by weight of water, said zeolite having a cation selected from the group consisting of sodium, potassium, lithium, ammonium and hydrogen and having a mean particle diameter of about 0.5 to about 12 microns, 15 to 20% of a carboxymethyl-oxysuccinate selected from the group consisting of water soluble alkali metal salts thereof and mix- -tures of said salts containing some unneutralized carboxymethyl-oxysuccinic acid; 5 to 25% of linear higher alkylbenzene sulfonate wherein the higher alkyl is of 10 to 16 carbon atoms; 3 to 18% of sodium silicate wherein the Na20:SiO2 ratio is in the range of 1:1 to 1:3.2; and 0.3 to 3% of an organic anti-redeposition agent selected from the group consisting of carboxymethyl cellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, lower alkyl cellulose and hydroxy-lower alkyl lower alkyl cellulose. In preferred aspects of the invention the molecular sieve zeolite is a hydrated or partial-ly hydrated type 4A molecular sieve zeolite~ in which the sodium aluminosili-cate is of SiO2:A1203 ratio of about 2 (on a molar basis, about one atom of silicon per atom of aluminum), the carboxymethyl-oxysuccinate is sodium carboxy-methyl-oxysuccinate, the linear higher alkylbenzene sulfonate is sodium tri-decylbenzene sulfonate, the sodium silicate is of Na20:SiO2 ratio of about 1:2.4, the anti-redeposition agent is sodium carboxymethyl cellulose and also contained is about 0.5 to 20% of higher fatty alcohol polyethoxylate having 6 to 15 ethoxy groups per mol and wherein the alcohol is of 12 to 18 carbon atoms and about 0.5 to 2% of sodium higher fatty acid soap wherein the higher fatty acid is of 12 to 18 carbon atoms.
- 4 ~
~7Z853 Also within the invention are methods of using the detergent compositions in washing laundry and fabrics.
The molecular sieve zeolites utilized in making the invented deter~ent compositions are water insoluble crystalline alluminosilicate zeolites of natural or synthetic origin which are characterized by having a network of uniformly sized pores in the range of about 3 to 10 Angstroms, preferably about ~ A
(nominal), which size is uniquely determined by the unit structure of the zeolite crystal. Of course, zeolites containing two or more such networks of different size pores can also be employed.
The molecular sieve zeolite should also be a univalent cation-exchanging zeolite, i.e., it should be an alumino-silicate containing a univalent cation such as sodium, potassium or lithium, when practicable, or of ammonium or hydroeen.
Preferably, the univalent cation associated with the zeolite molecular sieve is an alkali metal cation, especially sodium or potassium, most preferably sodium.
Crystalline types o~ zeolites utilizable as molecular sieves in the invention, at least in part, include zeolites o~
the following crystal structure groups: A, X~ Y, L, mordenite and erionite. Mixtures of such molecular sieve zeolites can also be useful, especially when type A zeolite, e.g., type ~A, is present. These preferred crystalline types of zeolites are well known in the art and are more particularly described in the text, Zeolite Molecular ~ieves, by Donald W. Breck, ~6~721~53 published in 1974 by John Wiley & 50ns. Typical commercially available zeolites of the aforementioned structural types are listed in ~able 9.6 at pages 747-749 of the Breck text.
Preferably the ~olecular sieve zeolite used in the invention is a synthetic molecular sieve zeolite. It is also preferable that it be o~ type A crystalline structure, more particularly described at page 133 of the aPorementioned text.
Especially good results are generally obtained in accordance with the invention when a type 4A molecular sieve zeolite is employed, wherein the univalent cation of the zeolite is sodium ~-and the pore size of the zeolite is about 4 Angstroms. The especially pre~erred zeolite molecular sieves are described in United States patent 2,882,243 which refers to them as Zeolite A.
Molecular sieve zeolites can be prepared in either a dehydrated or calcined form, the latter ~orm containing ~rom less than about 1.5% to about 3% of moisture, or in a hydrated or water loaded ~orm, which contains additional water of hydration and adsorbed water in sn amount up to about 30 to 36%
of the zeolite total weight, depending on the type of zeolite employed. Normally a completea hydrated type 4A synthetic zeolite will be o~ the ~ormula ( a20)6 (A1203)6 (SiO2)12 27 H20 or Nal2(A102 Si2)12 27 H2 . , .
: ~
- 6 - ~
` ~' : .
, ~al72853 when completely molecularly hydrated. ~owever, this product can still adsorb or absorb additional moisture so that the upp~r limit in moisture content is not about 22%,as calculated, but may be higher. Preferably, hydrated or partially hydrated ~orms of the molecular sieve zeolite are employed in the practice of this invention and these usually have a ~ater content of 18 to 28.5%, e.g., 20 to 22%. The manufacture of such crystals is well known in the art. For example, in the preparation o~ 1 Zeolite A, referred to above, the partially hydrated or hydrated zeolite crys-tals that are formed in the crystallization medium (such as hydrous amorphous sodium aluminosilicate gel) are made without the high temperature dehydration (calcining to 3% or ~ `
less water content) that is normally practiced in preparing such crystals for use as catalysts, e.g., cracking catalysts. The preferred form of zeolite in partially ~ydrated ~orm can be recovered by filtering o~f the crystals from the crystallization n~edlum and drying them in air at ambient temperature to ~luch an extent that the water content thereof is as desired.
Usually the molecular sieve zeolite should be in finely divided condition, such as crystals (amorp~ous or poorly crystalline p~rticles may also ~ind some use) having mean particle diameters in the range of about 0.5 to about 12 microns, preferably 5 to 9 microns and especially about 5.9 to 8.3 microns9 e.g., 6.4 to 8.3 microns.
The CMOS constituent o~ the present detergent compositions, carboxymethyl-oxysuccinate, normally employed as 1~7Z85.~
a water soluble salt, such as an aIkali metal salt, e.g., sodium carbox~methyl~oxysuccinate. ~he degreeofneutralization oP this supplementary builder may vary and in some cases some unneutralized carboxymethyl-oxysuccinic acid may be present.
However, normally the carboxyl groups will be converted to sPlt form before formulation of the detergent ~roduct, during such formulation or during washing with the composition. All the carboxyls of the CMOC are preferably neutralized, as with a sodium-containing base, to make them more effective as calcium sequestrants but it is within this invention to utilize partially neutralized CMOS, too. Thus, the mono- and di-salts and mixtures averaging mono-, di- and intermediate salts (including those intermediate di- and tri-) are also utilizable. While C~IOC in its sodium salt form i9 highly preferred as the auxiliary builder of this invention which cooperates with the zeolite and silicate to give the present detergent products superior properties, it is also contemplated that the CMOC may be substituted in part, e.g., up to 50%, by other builders of similar chemical structure. Thus, instead of the carboxymethyl-oxy substitution on the succinic acid, carbox~ethyl-oxy, carboxypropyl-oxy and carboxyisopropyl-oxy substitutions may be utilized and instead of succinic acid, comparable acidic compounds such as malonic acid, glutaric acia and adipic acid, may be employed (with the different substitutents on such acids, too) so long as they are operative. However, the _ 8 -.
.
.
~72853 use of CMOS is highly preferred and it will normally be employed as a sodium salt, preferably the trisodium and/or disodium salt.
The linear higher alkylbenzene sulfonate deter-gent will usually b e of 10 to 16 carbon atoms, preferably 12 to 14 carbon atoms and most preferably about 13 carbon atoms and will normally be neutralized with a suitable alkaline mate-rial, of which the most preferred are such s~hich result in alkali metal linear higher alkylbenzene sulfonates being produc-ed, preferably the sodium salts of the linear higher alkyl-benzene sulfonic acid. Other synthetic anionic organic deter- ;
gents may be present with the linear higher alkylbenzene sul-fonates but normally will only constitute a minor proportion of the total anionic detergent content of the present compositions.
Such supplementing anionic detergents may be of 8 to 26, preferably 12 to 22 carbon atoms per molecule and usually will include an alkyl or other aliphatic chain containing about 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms and most preerably will be straight chain alkyl. Such anionic detergents include the alpha-olefin sulfonatesJ paraffin sulfonates, ethoxy-lated alcohol sulfates, alkyl sulfates and sulfated higher alkyl phenyl polyoxyethylene ethanols, all preferably as alkali metal salts, such as the sodium salts. A list of such detergents is found in United States patent 3,~37,339. The water soluble higher fatty acid soaps, such as the sodium soaps of higher fatty , ~. . .
_ g _ , .~ .
~)728S3 acids of 12 to 18 carbon atoms may also be employed as anionic detergents in the present compositions.
Nonionic detergent compounds are often utilized in the present detergent compositions in mixture with a linear higher alkylbenzene sulfonate de-tergent and with any other suitable supplementing anionic detergent present. The nonionics will normally be lo~er aIkylene oxide condensation products, such as polyethylene oxides, which may sometimes have polypropylene oxide present too but only to such an extent that the product is still wat.er soluble. Preferred examples of such materials are the higher fatty alcohol-polyethylene oxide condensates wherein the higher fatty alcohol is of 10 to 18 carbon atoms, preferably 12 to 15 carbon atoms and the ethylene oxide portion thereof is a chain of 3 to 30 ethylene oxide units, preferably 6 to 15 ethylene oxide units and more preferably, about 10 to 13 ethylene oxide units. For example, a preferred nonionic detergent of this type is Neodol*45-11, manu~actured by Shell Chemical Comp~ny, wh~ch i6 a hi~her fatty alcohol polyethoxy-ethanol containing about 11 ethylene o~ide groups per mole (includin~ the ethoxy of the ethanol) ~nd having an average of about 14 to 15 carbon atoms in the higher fatty alcohol. Other primary alcohol condensation products include Plurafac*B-26 and Alfonic*1618-65. ~ergitol*15-S-9, made by Union Carbide Corpora-tion, exemplifies the suitable secondary alcohol condensation products with ethylene oxide. Also useful are similar ethy].ene oxide condensates of phenols, such as of nonyl phenol or isooctyl phenol, knoun as Igepals*, made by GAF Corporation, but these are not preferred.
In the present compositions there may also be em-ployed any o~ a number o~ suitable amphoteric and cationic detergents *Trademark - 10 -, . - . : - --~L~7Z85~
which are well known and, like the snionic and nonionic detergents, builders, adjuvants and other intended components of the present compositions, are described in the text Surface Active Agents and Detergents, Vol. II, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, Inc., especially at pages 25-138, and in Deter~ents and Emulsifiers, 1969-1973 Annuals, by John W. McCutcheon.
The sodium silicate component of the invented composition is one of Na20:SiO2 ratio in the range of 1:1 to 1:3.2, preferably 1:2 to 1:2.6 and most preferably about 1:2.4, e.g., 1:2.35. Such a compound is especially useful in -the present compositions for its combination anti-corrosion and building effects in con~unction with the zeolite molecular sieve and CMOS. The silicate is espec~ally good as a builder in wash waters containing magnesium ions and thereby usefully complements the other builder materials under u5ual washing conditions.
The w3e of an anti-redepositLon agent in the invented compositions is especially important because o~ the presence in the wash waters of insoluble, depositable particulate ma~erial, including the molecular sieve zeolite. Of the known anti-redeposition agents the most preferable to employ is sodium carboxymethyl cellulose but also useful, either as partial or complete substitutes for the sodium carboxymethyl ~ ;
cellulose (and only minor substitution is preferred) are ~
-- 11 -- , ~Lal728S3 polyvinyl alcohol, pol~vinyl acetate (which hydrolyzes to the alcohol), polyvinyl pyrrolidone, lower alkyl celluloses, e.g., methyl cellulose, ethyl cellulose, and hydroxy-lower alkyl lower alkyl celluloses, e.g., hydroxypropyl methyl cellulose, hydroxyethyl ethyl cellulose. In such latter cellulose compounds the lower alkyl groups are usually of 1 to 3 carbon atoms.
In addition to the molecular sieve zeolites, CMOS
and silicate, other builder salts may also be present in the invented compositions. Normally these are water soluble and are alkali metal salts, preferably the sodium and potassium salts o~ inorganic acids3 e.g., sodium carbonate, potassium bicarbonate~ borax, pentasodium tripolyphosphate and tetra-sodium pyrophosphate. However, the phosphates and borax are often preferably omitted ~or ecologica]. reasons. Organic builders may also be utilized in the present compositions, such as trisodium nitrilotriacetate or NTA (which is still not approved for general use in detergents~, sodium citrate, potassium gluconate and hydroxyethyl iminodiacetate, disodium salt. 0~ course, ~iller salts, such as sodium sul~ate and sodium chloride, are normal constituents o~ detergent composi-tions and may be employed. -Various ad~uvants may be present for their special activities, such as enzymes, e.g., proteolytic enzymes (proteases) and amylotic enzymes (amylase); hydrotropes, e.g., sodium toluene sulfonate; wetting agents; flow-improving , :: ' ' :, .
1~7Z~35;~
agents, e.g., clays ~although the molecular sieve zeolite usually performs such functions satisfactorily in the proportion employed); bactericides, fungicides, fluorescent brighteners;
dyes; pigments; perfumes; emollients; stabilizers; fillers;
coating agents; and softeners. When bleachesJ e.g., sodium perborate, sodium percarbonate, and activators for bleaching are used they will usually be present in greater quantities than other adjuvants.
The proportions of the various components of the invented compositions should be held within the following described ranges for good activities. The product should com-prise ~and often may consist essentially of)preferably 15 to 20% of molecular sieve zeolite, more preferably about 17%;
tlle same ranges of percentages for CMOS; 5 to 25% of linear i`
higher alkylbenzene sulfonate, preerably 8 to 12% and more preferably about 10%; 3 to 18% of sodium silicate, preferably 5 to 15% and more preferably about 8%; and 0.3 to 3%J pre-ferably 0.3 to 1% and more preerably about 0.5~ of anti-redeposition agent. The ratios of molecular sieve zeolite :
CMOS : linear higher alkylbenzene sulfonate ; sodium silicate : -anti redeposition agent will usually be in the range of 1 : 0.5 to 2 : 0.2 to 1 : 0.3 to 2 : 0.02 to 0.2, preferably 1 : 0.7 to 1.2 : 0.4 to 0.8 : 0.3 to 0.7 : 0.02 to 0.1 and most pre-ferably about 1 : 1 : 0.6 : 0.5 : 0.03. When nonionic detergent is present in the formulation :-.... .
~ 13 -- ~
1~:97Z853 it will normally be ~rom 0.5 to 20% o~ the product, preferabl~ 0.5 to 2.5%
thereof and most preferably will ~e about 2~. When soap is present it will usually be in a proportion from 0.3 to 3%, preferably 0.5 to 2% and most preferably about 1%. Filler content will generally be in the range of 15 to 60%, preferably 25 to ~5% and most pre~erably about 35%. Moisture content may be from 0.5 to 15%, usually being 2 to 10% and preferably 3 to 8%, e.g., 7%, as "free moisture".
Any usual adjuvants present will normally total about 1 to 10%, with individual ad~uvants generally being in the range of 0.01 to 5%. For example, the content of fluorescent brighteners or optical dyes may be in the range o~ 0.01 to 2%, normally being about 0.5 to 1.5%. The t ~ of ad~uvants is preferably in the range of 1 to 5%, such as 2 to ~% and typical-ly about 2.5% thereof may be present and will include perfumes, colorants, flow promoting compounds and optionally, fungicides, bactericides and emol-lients. I~ bleaches are present in these detergent compositions they will normally be from 5 to 30%, including activators for bleaching percompounds, and the~proportions of other components will ble reduced accordingly. Of course, mlxtures of dif~erent types of individ~ual components within the in-vention may be used, too.
~he various components of the detergent compositions m~y be blended together by admixing powdered compounds but preferably crutcher mixes of most of the components are spray dried, spray cooled, drum dried or otherwise converted to globular "spray dried" form. Alternatively, various components may be co-size-reduced to the desired particle size ranges. ~ormally, per-fume, nonionic detergent, flow promoting agent and any heat-sensitive com-porents will be post-added to tumbling spray dried detergent composition.
However, in some cases it may be desirable to promote ~low of tbe product by post-adding a proportion of the molecular sieve zeolite, e.g., 10 to 25% of the amount o~ molecular sieve ~eolite in the final product The globular particles of detergent compositions may be classified or sieved so that over 90%, preferab.~y over 95% and most preferably, all tbereof passes through a ~o. 8 or No. 10 United States Standard Sieve Series sieve and less than 10%, : ' . . : , ~7;~8'~3 pre~erably less than 5% and most preferably, 0% passes through a No. 100sieve. The rest of the product, which may be post-added, if in the solid state, will normally be in powder form, with the molecular sieve zeolite powder component being of the size previously mentioned, e.g., from 5 to 9 microns in diameter, and the other po~dered products being such that they will pass through a ~o. 100 sieve and fail to pass a ~o. I~oo sieve, pref-erably pasfing through a No. 1~0 sieve and resting on a No. 325 sieve. When the nonionic detergent is in liquid form or may be readily liguefied, it may be desirable to spray it onto the surfaces of the tumbling detergent globule-powder mixture.
The washin~methods of this invention may be carried out at various pH's and concentrations of the detergent composition in washing liquid medium but normally the pH will be in the range of 8 to 12, preferably 8.5 to 10.5 ancl most preferably 9 to 10.5. The concentration of the detergent composi-tion in the aqueous washing medium, which will usually be ordinary tap water, will normally be from 0.05 to 2%, preferably being about 0.1 to 1%. Most preferably, such concentration will be about 0.15% in the United States and abo~lt o.8% in European countries wherein high concentrations of detergent and low volumes of wash water have been employed in the conventional washin~
machines. Usually the laundry : wash water ratio will be from 0.03 to 0.2, preferabl~ 0.04 to 0.1~ e.g., 0.05 or o.o6 for United States laundry practices and about one to five times these ra-tios, e.g., about three times such rat~os, for European practices. ~aterials washable with the invented com-positions include cottons, polyesters, cotton-polyester blends, e.g., 55:45 blends, permanent press fabrics and all usual commercial fabrics.
~he present compositions are employed in the same manner as com-parable commercial heavy duty laundry detergents. Thus, they may be used for cold, warm and hot water washing, usually in the temperature range of 10 to 70 C. Excellent cold and warm water washings of ~arious types of fabrics result, using ordinary automatic washing machines and normal washing times, 3 to 45 minutes, preferably being from 5 to 20 minutes in the United States and from 20 to 40 minutes according to European practices.
, ,. , . : :. . .
1~72853 Various advantages of the invented compositions have already been mentioned. The presence of the molecular sieve zeolite appears to help to prevent staining o~ ~hite or light goods ~ith stains which might be removed from colored goods or laundry containing colored soils. In such cases, in the presence of the CMOS and other detergent composition constituents, the molecular sieve zeolites appear to preferentially adsorb the color bodies ;
and thereby prevent them from being deposited on the white or lighter colored goods, resulting in a lesser amount of discoloration thereof. Also, the lowered content of molecular sieve zeolite results in less deposition thereof on the clothing and the proportion of anti-redeposition agent present is capable of maintaining most of the molecular sieve zeolite in suspension in the wash water so that it does not become entrapped in the fabrics being cleaned (which could occur during rinsing). The presence of the linear alkylbenzene sulfonate detergent appears to assist in maintaining the sus-pension of the molecular sieve zeolite, too. Of course, the combination of various types of builders which are "sequestrants" for different types of h~ dnesses favors ~etter wnshing by the anionic detergent (and accompanying nonionic detergent, when employed). Thus, there are sienificant coactions between the various components in the proportions in which they are employed in the present detergent compositions.
~ he invention will be further illustrated by the following ex-amples. Unless otherwise indicated all parts therein and in the specifica-tion are by weight a~d all temperatures are in C.
EXA~PIE 1 A preferred detergent composition of this invention is made by spray drying an aqueous crutcher mix of the components thereof and containing about 60% of solids, in a countercurrent spray tower utilizing drying air at about 250 C,, to a moisture content of about 6.5% and then spraying 0.5% of perfume onto tumbling surfaces thereof. The perfumed spray dried detergent composition includes, on a final product basis, about 10% of sodium linear tridecyl benzene sulfonate, 17% of type I~A molecular sieve zeolite (the SiO2:A1203 mol ratio of which is 2 and which contains 20% of moisture, is of ~`~
- ~:
~C~7;Z~Si3 pore sizes of about 4 ~ gstroms diameter and is of particle si~es in the range of 5.9 to 803 microns in diameter), 17% of sodium CMOS (trisodium salt), 0.5% of sodium carboxymethyl cellulose, 2% o~ ~eodol ~5-ll (higher :-fatty alrohol polyethoxyethanol of about ll ethoxy groups per mol and in which the higher fatty alcohol is of 14 to 15 carbon atoms per mol), 1% of higher fatty acid soap ~herein the higher fatty acid i5 a mixture of hydro-genated coconut oil ana hydrogenated tallow in 1:4 ratio, 35% of sodium sulfate (as the anhydrous form), 8%of sodium silicate (Na20:SiO2 = 1:2.35) and about 3% of various ad~uvants (fluorescent brighteners, perfume, stabili2er, free oil [impurities in materials charged] and colorants). The particle sizes of the spray dried beads are in the range of lO to 100 mesh, United States Standard Sieve SPries. The CMOS, sulfate and CMC, as charged to the crutcher, are powders of particle sizes such that they pass through a No. 140 sleve and rest on a No. 325 sie~e, United States Standard Sieve Series.
The detergent composition made i8 substantially homogeneous, free-flowing and non-dusting, possibly in part due to the adsorption cf any excess moisture in the spra~ dried product by the zeolite molecular sie~e. Also, the product is substantially non-tacky and non-caking under ordinary storage conditions.
In test washing of mixed laundr~ having an artificial test soil deposited thereon, whlch laundry is composed of' test swatches of cotton, cotton-polyester and permanent press treated cotton-polyester fabrics, the detergent concentration in the wash water is 0.15%, the water employed has 150 parts per million of hardness (the clacium : magnesium hardness ratio, calculated as calcium carbonate, being 3:2), the temperature is maintained at 49C. and washing is continued for ten minutes in a laboratory Tergo-tometer ~ washing machine. At the end of washing the wash water has a pH
of 9.2. The test f`abrics washed are rinsed and dried in the normal manner and are read for whiteness (Rd on the Gardner Color Difference Meter). The Rd for the pre~erred experimental composition described is 50Ø Thls indi-cates that the cleaning power of the detergent composition is superîor to : . . . , . , . . : . .
~a~7z853 that of a similar composition, made the same way~ in which the combinationof the molecular sieve ~eolite and CMOS is replaced by an equal weight of pentasodium tripolyphosphate ( Rd = 48.7); the molecular sieve zeolite ( Rd = 45.9); CMOS ( Rd = 48.5); equal parts of type 4A molecular sieve zeolite and of pentasodium tripolyphosphate ( Rd = 46.8); equal parts of the molecular sieve zeolite and of sodium citrate ( Rd = ~.5), and equal parts of the molecular sieve Peolite and sodium tartrate ( Rd = 41.0).
In practical laundry tests the preferred composition is also especially useful in removing various types of soils from the lalmdry. How-ever, in such tests the water temperature ranges from 15 C. to 65C., thehardness thereof is from 50 to 250 parts per million of calcium carbonate (mixed clacium and magnesium hardness), the washing times are from 5 to ~5 minutes, the machines employed are top loading and side loading, the deter-gent composition : laundry weight ratio is from 0.01 to 0.1 and the laundry :
wash water ratio is from 0.03 to 0.2. No ob~ectionable deposits of molecular sieve zeolite are found on laundry which is machine washed and subsequently line dried and of course, no such deposits are found on such laundry which is dried in an automatic clothes dryer.
The whitening power of the composition can be further improved by replacing half of the quantity Or sodium sulfate present (17.5%) with penta-sodiu~ tripolyphosphate, when such compound may be employed without violation of l&w and without adverse effects on the ecology. Apparent brightness is improvable when fluorescent brighteners are included in the formula as part of the ad~uvant composition, especially when there is present a stilbene fluorescent brightening compound, such as Tinopal ~ RB~ (Geigy), preferably with Tinopal 5B~I Conc. in lesser proportion, the total proportion of the ;
fluorescent brighteners being about 1%. Stain removal and soil removal are also improved by the addition to the composition of about 1% of Alcalase ~ ;
proteolytic enzyme. Further useful effects in removing stains and soils are obtainable when a per compound such as sodium perborate tetrahydrate is present, usually as a ma~or replacement for the sodium sulfate, e.g., con-stituting about 20% of the detergent product. Such perco~pound is post-.`' :
' . ' ' ' ' ' ': '' .- ~: ~ ' ~7z1353 added to the spray dried product.
In variations of the above formula for the preferred invented product the ~eodol and soap are omitted. In such cases the invented com-positions are still better in washing effects than the various controls described, from ~hich such components have also been removed. In other variations of the formulation 20% of the linear aIkylbenzene sulfonate con-tent is replaced by sodium higher fatty alcohol sulfate in one experiment, 30% of it is replaced by sodium paraffin sulfonate in another case and in another instance 25% of it is replaced by alphaolefin sulfonate of essen-tially the same chain length. In all such cases satisfactory detergents of .
desirable characteristics, such as those described, are obtained. Such isalso the situation ~Then the proportion of sodium silicate present is in-creased to 15% in the final product.
The compositions of Example l are made but with the substitution of type ~A molecular sieve zeolite which i9 completely molecularly hydrated (22%
of water of crystallization, corresponding to 27 mols H20 per mol zeolite), partially hydrated such molecular sieve zeolite containing about half as much of water o~ hydration and an anhydrous type 4A molecular sieve zeolite. Use-ful detergent products result in all such cases.
The compositions oP this example are ~urther varied by replacin~
the trisodium CMOS employed with disodium CMOS ~nd with monosodium CMOS and by partially replacing it (20%) with carboxymethyl-oxysuccinic acid. UsePul detergents of desirable cleaning power are also obtained. ~;
.. .
In a further variation of these formulas sodium silicates of '. :'' ...
~a20:SiO2 ratios oP 1:2.0 and 1:2.6 are employed and good detergents sim-ilarly result. ~his is also the case ~hen sodium carboxgmethyl cellulose is replaced, to the extent of half the content thereof, with polyvinyl alcohol, ~ `
polyvin~l pyrrolidone~ hydroxypropylmethyl cellulose and methyl cellulose, respectively. ~owever, it is considered that sodium CMC makes the best detergents, those having the best soil anti-redeposition properties, and therePore it is preferred to use it alone.
. ' ' ~:, `
.
~0~28S3 Instead of the type 4A molecular sieve zeolite there are sub-stituted the same quantities of types X and Y molecular sieve zeolites in the formulas of Examples 1 and 2. The products resulting are useful deter-gents by the tests described but for best detereency and physical properties it is considered most desirable to utilize the type 4A molecular sieve zeolite which is either hydrated or partially hydrated~ Anhydrous forms of the various zeolites, unless they are hydrated during the manufacture of the detergent composition, take additonal time durine the washing operation to be hydrated first before they are able to effectively carry out their seques-tering and building functions. Thus, they take longer to act and therefore may be less effective in some instances.
The proportions of the various components of the compo~itions of Examples 1-3 are varied within the ranges and ratios given in this specifica-tion, normally beine chan~ed -30%, ~ 0% and -10%, within such ranges. ~he products made are useful detergents, suitable for employment in various cleaning operations. Of such detergents, those which contain no phosphorus or are sub3tantially free of phosphorus (usually containing less than 1% of phosphorus) are preferred, to comply with anti-eutrophication laws and reg-ulations. --~ he formulations of the previous examples are mndified by replacing the nonionic detergent, when present, with a comparable nonionic detergent, Plurafac B-26 ana alternatively~ with Alfonic 1618-65. In variations of the manufacturing proceduse, the nonionic detergent is melted and sprayed onto the surfaces of the tumbling spray dried components. GoGd detergents result. -i ~his iB also the csse when half of the sodium sulfate filler content is re-placed by sodium chloride. In other variations of the manufacturing methods the molecular sieve, C~OS and ~MC are post-added to spray dried besds of the rest o~ the product components and the detergent composition resulting is also superior to control compositions based on pentasodium tripolyphosphate _ 20 -. , - : , . ~ :. . .
(wheretn the STPP is present in quantity equal to the sum of the CMOS and molecular sieve zeolite). The detergent composition is also made by co-size-reducing the various powders to the 10 to 100 mesh range (the zeolite adhering to the larger sized particles). The products so made are also acceptable detergents, comparable in performances to those previously described and superior to the various controls mentioned.
!~ -The invention has been described with respect to various illustra-tions and embodiments thereof but is not to be limited to these because it is evident that one of skill in the art will be able to use substitutes and equivalents without departing from the spirit of the invention.
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Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A heavy duty laundry detergent substantially free of phosphorous comprising 15 to 20% by weight of a water insoluble aluminosilicate molecular sieve zeolite capable of sequestering soluble calcium ions in wash water which is selected from the group consisting of A, X, Y, L, mordenite and erionite and containing from about 1.5% to about 36% by weight of water, said zeolite having a cation selected from the group consisting of sodium, potassium, lithium, ammonium and hydrogen and having a mean particle diameter of about 0.5 to about 12 microns, 15 to 20% of a carboxymethyl-oxysuccinate selected from the group consisting of water soluble alkali metal salts thereof and mixtures of said salts containing some unneutralized carboxymethyl oxysuccinic acid; 5 to 25% of linear higher alkylbenzene sulfonate wherein the higher alkyl is of 10 to 16 carbon atoms; X to 18% of sodium silicate wherein the Na20:Si02 ratio is in the range of 1:1 to 1:3.2; and 0.3 to 3%
of an organic anti-redeposition agent selected from the group consisting of carboxymethyl cellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, lower alkyl cellulose and hydroxy-lower alkyl lower alkyl cellulose.
of an organic anti-redeposition agent selected from the group consisting of carboxymethyl cellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, lower alkyl cellulose and hydroxy-lower alkyl lower alkyl cellulose.
2. A detergent composition according to claim l wherein the molecular sieve zeolite is a sodium aluminosilicate of Si02:A1203 ratio of about 2, and which contains from 0.5 to 20% of higher monohydric alcohol polyethoxy-late having 6 to 15 ethoxy groups per mol and wherein the alcohol is of 10 to 18 carbon atoms.
3. A detergent composition according to claim 2 wherein the zeolite is a type A molecular sieve zeolite, the carboxymethyl-oxysuccinate is sodium carboxymethyl oxysuccinate, the linear higher alkylbenzene sulfon-ate is sodium linear higher alkylbenzene sulfonate, the alkyl of which is of 12 to 14 carbon atoms, the higher monohydric alcohol polyethoxylate is one wherein the ethoxy groups are in a chain and which contains about 10 to 13 ethoxygroups per mol, the sodium silicate is of Na20:Si02 ratio in the range of about 1:2 to 1:2.6 and the organic anti-redeposition agent is sodium carboxymethyl cellulose.
4. A detergent composition according to claim 3 wherein the zeolite is hydrated type 4A molecular sieve zeolite.
5. A detergent composition according to claim 3 in globular form with the particles thereof being of such sizes as to pass through a No. 8 sieve and rest on a No. 100 sieve.
6. A detergent composition according to claim 5 which is substan-tially free of phosphorus.
7. A detergent composition according to claim 6 which is free of inorganic phosphate and carbonate builder salts.
8. A method of washing laundry which comprises contacting said laundry with an aqueous medium containing 0.1 to 1% by weight of the detergent composition which includes 15 to 20% by weight of a water insoluble molecular sieve zeolite selected from the group consisting of A, X, Y, L, mordenite and erionite and containing from about 1.5% to about 36% by weight of water, said zeolite having a cation selected from the group consisting of sodium, potas-sium, lithium, ammonium and hydrogen and having a mean particle diameter of about 0.5 to about 12 microns, 15 to 20% of a carboxymethyl-oxysuccinate selected from the group consisting of water soluble alkali metal salts there-of and mixtures of said salts containing some unneutralized carboxymethyl-oxy-succinic acid; 5 to 25% of linear higher alkylbenzene sulfonate wherein the higher alkyl is of 10 to 16 carbon atoms; 3 to 18% of sodium silicate wherein the Na20:Si02 ratio is in the range of 1:1 to 1:3.2; and 0.3 to 3% of an organic anti-redeposition agent selected from the group consisting of carboxy-methyl cellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, lower alkyl cellulose and hydroxy-lower alkyl lower alkyl cellulose.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64079375A | 1975-12-15 | 1975-12-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1072853A true CA1072853A (en) | 1980-03-04 |
Family
ID=24569725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA267,486A Expired CA1072853A (en) | 1975-12-15 | 1976-12-09 | Laundry detergent composition and use |
Country Status (7)
| Country | Link |
|---|---|
| AU (1) | AU510677B2 (en) |
| BE (1) | BE849437A (en) |
| CA (1) | CA1072853A (en) |
| DE (1) | DE2656251A1 (en) |
| DK (1) | DK563876A (en) |
| FR (1) | FR2335590A1 (en) |
| ZA (1) | ZA767282B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2852285A1 (en) * | 1978-12-02 | 1980-06-12 | Henkel Kgaa | LOW-PHOSPHATE FRUIT SALT MIXTURE AND THEIR USE IN DETERGENT AND CLEANING AGENTS |
| US4261941A (en) * | 1979-06-26 | 1981-04-14 | Union Carbide Corporation | Process for preparing zeolite-containing detergent agglomerates |
| US4687592A (en) * | 1985-02-19 | 1987-08-18 | The Procter & Gamble Company | Detergency builder system |
| CA1337041C (en) * | 1985-10-09 | 1995-09-19 | Brett Alan Evans | Granular detergent compositions having improved solubility |
| GB8620733D0 (en) * | 1986-08-27 | 1986-10-08 | Procter & Gamble | Detergency builders & built detergents |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4605509A (en) * | 1973-05-11 | 1986-08-12 | The Procter & Gamble Company | Detergent compositions containing sodium aluminosilicate builders |
| DE2433485A1 (en) * | 1973-07-16 | 1975-02-06 | Procter & Gamble | ALUMINOSILICATE ION EXCHANGERS SUITABLE FOR USE IN DETERGENTS |
| ES437284A1 (en) * | 1974-05-07 | 1977-07-01 | Colgate Palmolive Co | Detergent compositions |
| US3985669A (en) * | 1974-06-17 | 1976-10-12 | The Procter & Gamble Company | Detergent compositions |
-
1976
- 1976-12-07 ZA ZA00767282A patent/ZA767282B/en unknown
- 1976-12-09 AU AU20428/76A patent/AU510677B2/en not_active Expired
- 1976-12-09 CA CA267,486A patent/CA1072853A/en not_active Expired
- 1976-12-11 DE DE19762656251 patent/DE2656251A1/en active Pending
- 1976-12-14 FR FR7637617A patent/FR2335590A1/en active Granted
- 1976-12-15 DK DK563876A patent/DK563876A/en not_active Application Discontinuation
- 1976-12-15 BE BE173287A patent/BE849437A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| AU2042876A (en) | 1978-06-15 |
| FR2335590A1 (en) | 1977-07-15 |
| FR2335590B1 (en) | 1981-12-11 |
| DK563876A (en) | 1977-06-16 |
| AU510677B2 (en) | 1980-07-10 |
| ZA767282B (en) | 1978-07-26 |
| BE849437A (en) | 1977-04-01 |
| DE2656251A1 (en) | 1977-06-16 |
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